Pattern Hardening Coating Agent

ABSTRACT

A pattern hardening coating agent useful in a method for forming a fine pattern, comprising: an addition copolymer comprising a repeating unit derived from a fluoro alkyl (meth)acrylic ester and a repeating unit derived from a glycidyl (meth) acrylic ester and an organic solvent.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a division of U.S. application Ser. No. 11/759,667 filed Jun. 7,2007, which claims the priority benefit under USC 119 of KR10-2007-0001407 filed Jan. 5, 2007, the entire respective disclosures ofwhich are incorporated herein by reference.

BACKGROUND OF THE INVENTION

The invention relates generally to a method for forming a fine patternin a semiconductor device.

In order to manufacture smaller semiconductor devices, patterns havebecome smaller. Research has been directed to developing resists andexposers for obtaining fine patterns.

Regarding exposers, KrF (248 nm) and ArF (193 nm) have been applied asan exposure light source , and attempts have been made to use shortwavelength light sources such as F2 (157 nm) or EUV (13 nm; extremeultraviolet light) or to increase numerical apertures (NA).

However, when new light sources such as F2 are applied, a new exposer isrequired, and increased manufacturing costs result. Also, the increaseof numerical apertures degrades the focus depth width.

Although an immersion lithography process with an immersion solutionhaving a high refractive index has been developed, it is difficult toapply the process on a mass production scale.

Meanwhile, a fine pattern having a resolution beyond the lithographylimit has been formed by a double exposure method. However, it isdifficult to secure margins of overlapping and arrangement, whichresults in excessive production cost and time.

SUMMARY OF THE INVENTION

Various embodiments of the invention are directed at providing a methodfor forming a pattern hardening film over a first photoresist patternalready formed. The method includes hardening a first photoresistpattern, forming a second photoresist film and performing an exposureand developing process to form a second photoresist pattern, therebyobtaining a fine pattern having a pitch finer than the lithographylimit.

According to an embodiment of the invention, a method for forming a finepattern of a semiconductor device includes the steps of: forming a firstphotoresist pattern over a semiconductor substrate having an underlyinglayer; coating a pattern hardening coating agent over the firstphotoresist pattern, thereby forming a pattern hardening film; forming asecond photoresist film over the resulting structure; and selectivelyexposing and developing the second photoresist film, thereby forming asecond photoresist pattern to be defined between neighboring firstphotoresist pattern.

The pattern hardening coating agent preferably includes: an additioncopolymer having a repeating unit derived from a fluoro alkyl(meth)acrylic ester and a repeating unit derived from a glycidyl(meth)acrylic ester a; and an organic solvent. The polymer preferablyhas a 2,2,3,4,4,4-hexafluorobutyl methacrylate repeating unit and aglycidyl methacrylate repeating unit. The organic solvent can be ahigher alcohol solvent having five or more carbon atoms. The coatingagent can further include 2-hydroxycyclohexyl p-toluensulfonate.

The pattern hardening coating agent preferably includes the polymer inan amount ranging from 1 to 5 weight parts, based on 100 weight parts ofthe coating agent.

The step of coating the pattern hardening coating agent preferablyincludes baking the pattern hardening coating agent at a temperatureranging from 150° C. to 300° C. for 30 seconds to 180 seconds.

The step of forming the first photoresist pattern preferably includes:coating a first photoresist composition over a semiconductor substratehaving an underlying layer, thereby forming a first photoresist film;selectively exposing the first photoresist film with an exposure energyranging from 10 mJ/cm2 to 200 mJ/cm2 using a first exposure mask;post-baking the resulting structure at a temperature ranging from 90° C.to 150° C. for 30 seconds to 180 seconds; and developing the resultingstructure.

The step of forming the second photoresist pattern preferably includesselectively exposing the second photoresist film with an exposure energyranging from 10 mJ/cm2 to 200 mJ/cm2 using a second exposure mask;post-baking the resulting structure at a temperature ranging from 90° C.to 150° C. for 30 seconds to 180 seconds; and developing the resultingstructure.

The second exposure mask is preferably same one as the first exposuremask, or it can be an additional exposure mask.

The processes for forming the first and second photoresist patterns arepreferably performed with immersion lithography equipment.

In one embodiment, a pitch between the first photoresist pattern is A,and a pitch between the second photoresist pattern is A/2.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1 a through 1 d are cross-sectional diagrams illustrating a methodfor forming a fine pattern in a semiconductor device according to anembodiment of the invention.

FIG. 2 is an NMR spectrum of a pattern hardening coating agent polymerobtained from Example 1.

FIG. 3 is an illustration of a fine pattern obtained from Example 3.

DETAILED DESCRIPTION OF THE SPECIFIC EMBODIMENT

Specific embodiments of the invention is described in detail withreference to the accompanying drawings.

FIGS. 1 a through 1 d are cross-sectional diagrams illustrating a methodfor forming a fine pattern in a semiconductor device according to anembodiment of the invention.

A hard mask layer 13 is formed over a semiconductor substrate 11 havingan underlying layer which includes a given lower structure. Ananti-reflection film 15 is formed over the hard mask layer 13.

A first photoresist composition is coated over the anti-reflection film15, and then baked at a temperature ranging from 90° C. to 150° C. for30 seconds to 180 seconds to form a first photoresist film (not shown).

Any suitable chemically amplified photoresist composition can be used asthe first photoresist composition in an immersion lithography process.

The first photoresist film is exposed with a first exposure mask havinga line pattern of pitch A by an exposure energy ranging from 10 mJ/cm2to 200 mJ/cm2 using immersion lithography equipment. The light source ofthe exposure process is selected from the group consisting of G-line(436 nm), i-line (365 nm), KrF (248 nm), ArF (193 nm), F2 (157 nm), andEUV (13 nm).

The resulting structure is post-baked at a temperature ranging from 90°C. to 150° C. for 30 seconds to 180 seconds, and developed with a 2.38wt % tetramethyl ammonium hydroxide (TMAH) aqueous solution to form afirst photoresist pattern 17.

A pattern hardening coating agent is coated over the first photoresistpattern 17, and baked at a temperature from 150° C. to 300° C. for 30seconds to 180 seconds to form a pattern hardening film 19.

The pattern hardening coating agent includes: an addition copolymerhaving a repeating unit derived from a fluoro alkyl (meth)acrylic esterand a repeating unit derived from a glycidyl(meth)acrylic ester, and anorganic solvent.

It is preferable that the polymer includes a 2,2,3,4,4,4-hexafluorobutylmethacrylate repeating unit and a glycidyl methacrylate repeating unit.

The repeating unit derived from a fluoro alkyl (meth)acrylic esterdissolves a higher alcohol solvent, and the repeating unit derived froma glycidyl (meth)acrylic ester serves as a cross-linking agent.

The polymer is present in an amount ranging from 1 to 5 weight parts,based on 100 weight parts of the coating agent. The cross-linkingreaction does not occur sufficiently when the polymer is present in theamount of less than 1 weight part, and the critical dimension CD ofphotoresist becomes larger when the polymer is present in the amount ofover 5 weight parts.

The organic solvent is one or more selected from the group consisting ofhigher alcohol solvents having five or more carbon atoms such asn-pentanol and 4-methyl-2-pentanol. The first photoresist pattern 17 isnot dissolved even when coated by the pattern hardening coating agent.The organic solvent can be the balance of the coating agent.

The pattern hardening coating agent may further include2-hydroxycyclohexyl p-toluenesulfonate as a in cross-linking catalyst.

A second photoresist composition is coated over the resulting structure,and then baked at a temperature ranging from 90° C. to 150° C. for 30seconds to 180 seconds to form a second photoresist film 21.

Any suitable chemically amplified photoresist composition can be used asthe second photoresist composition in the immersion lithography process.

Although the second photoresist composition is coated, the firstphotoresist pattern 17 is hardened by the pattern hardening film 19 sothat the pattern 17 is not changed by the second photoresistcomposition.

The second photoresist film 21 is exposed with a second exposure maskhaving a line pattern of pitch A by an exposure energy ranging from 10mJ/cm2 to 200 mJ/cm2 using immersion lithography equipment.

The second exposure mask can be the first exposure mask displaced aspecified distance, or it can be an additional exposure mask.

The resulting structure is post-baked at a temperature ranging from 90°C. to 150° C. for 30 seconds to 180 seconds, and developed with a 2.38wt % TMAH aqueous solution to form a second photoresist pattern 23having individual elements between individual elements of the adjacentfirst photoresist pattern 17. Both the first and second photoresistpatterns 17, 23 have a pitch A that is the minimum size limit of thelithography process. The staggered arrangement of the first and secondphotoresist patterns 17, 23 results in a composite photoresist patternhaving a reduced pitch A/2 (i.e., a pitch smaller than the lithographylimit).

The second photoresist pattern 23 can be formed between the firstphotoresist pattern 17 because its original shape is preserved by thepattern hardening film even after the exposure and developing process.

According to another embodiment of the invention, the method stepsrepresented by FIGS. 1 a through 1 d are repeated at least two or moretimes, thereby obtaining an even finer pattern.

EXAMPLE 1 Preparation of a Pattern Hardening Coating Agent Polymer

To a round flask (250 mL) were added 2,2,3,4,4,4-hexafluorobutylmethacrylate (13.2 g), glycidyl methacrylate (8 g),azobisisobutyronitrile (AIBN) (0.4 g) as a polymerization initiator, andpropylenegylcol methyl ether acetate (PGMEA) (100 g). The resultingmixture was reacted under a nitrogen atmosphere for 8 hours. Afterreaction, the resulting polymer was precipitated in n-hexane (1000 mL)and dehydrated in a vacuum to obtain a pattern hardening coating agentpolymer according to the invention (yield: 91%). FIG. 2 is an NMRspectrum of the resulting polymer.

EXAMPLE 2 Preparation of a Pattern Hardening Coating Agent

In n-pentanol (500 g) were dissolved the pattern hardening coating agentpolymer (10 g) obtained from Example 1 and 2-hydroxycyclohexylp-toluensulfonate (0.3 g) to obtain a pattern hardening coating agentaccording to the invention.

EXAMPLE 3 Formation of a Fine Pattern Formation of a First PhotoresistPattern

An immersion photoresist composition DHAI102 (produced by DongjinChemical Co.) was coated over a wafer, and pre-baked at 100° C. for 60seconds to form a first photoresist film. The first photoresist film wasexposed with a mask having an 80 nm half pitch by an exposure energy of37 mJ/cm2 using immersion lithography equipment. The resulting structurewas post-baked at 100° C. for 60 seconds, and developed with a 2.38 wt %TMAH aqueous solution, thereby obtaining a 30 nm first photoresistpattern.

Formation of a Pattern Hardening Film

The pattern hardening coating agent obtained from Example 2 was coatedover the first photoresist pattern, and pre-baked at 170° C. for 90seconds to obtain a pattern hardening film so that the first photoresistpattern increases to 40 nm.

Formation of a Second Photoresist Pattern

An AIM5076 photoresist composition (produced by JSR Co.) was coated overthe above resulting structure, and pre-baked at 100° C. for 60 secondsto form a second photoresist film. The second photoresist film wasexposed with a mask having an 80 nm half pitch by an exposure energy of38 mJ/cm2 using immersion lithography equipment. The resulting structurewas post-baked at 100° C. for 60 seconds, and developed with a 2.38 wt %TMAH aqueous solution, thereby obtaining a 40 nm second photoresistpattern.

Since the elements of the second photoresist pattern were formed betweenadjacent elements of the first photoresist pattern, the resultingcomposite pattern was formed to have a 40 nm half pitch with a maskhaving a 80 nm half pitch (see FIG. 3). The mask used in the secondexposure process was the same mask used in the first exposure process,although it was shifted a specified distance in between the two exposureprocesses.

As described above, in a method for forming a fine pattern of asemiconductor device according to an embodiment of the invention, apattern hardening film is formed over a first photoresist pattern whichhas been already formed. In other words, a first photoresist pattern ishardened, and a second photoresist film is formed. An exposure anddeveloping process is performed to form a second photoresist pattern,thereby obtaining a fine pattern having a pitch finer than the alithography limit. Furthermore, the above method can be repeated severaltimes to obtain an even finer pattern.

The above embodiments of the invention are illustrative and notlimiting. Various alternatives and equivalents are possible. Theinvention is not limited by the lithography steps described herein. Noris the invention limited to any specific type of semiconductor device.For example, the invention may be implemented in a dynamic random accessmemory (DRAM) device or a non-volatile memory device. Other additions,subtractions, or modifications that are obvious in view of the presentdisclosure and are intended to fall within the scope of the appendedclaims.

1. A pattern hardening coating agent comprising: an addition copolymercomprising a repeating unit derived from a fluoro alkyl (meth)acrylicester and a repeating unit derived from a glycidyl (meth) acrylic esterand an organic solvent.
 2. The agent according to claim 1, wherein theaddition copolymer comprises a 2,2,3,4,4,4-hexafluorobutyl methacrylaterepeating unit and a glycidyl methacrylate repeating unit.
 3. The agentaccording to claim 1, further comprising 2-hydroxycyclohexylp-toluensulfonate.